Solid amine adducts

ABSTRACT

The invention relates to a process for preparing an amine adduct, in which a polyamine component (A), a polyester component (B) and a hydrocarbon component (C) are reacted. The amine adduct is of particularly good suitability as a wetting agent and dispersant, especially for coatings and plastics applications.

The present invention relates to a process for preparing an amine adductand the use of the amine adduct.

Wetting agents that exist in a form dissolved or dispersed in a liquidreduce the surface tension or the interfacial tension and thus increasethe wetting capacity of the liquid. In this way, in many instances,wetting agents make surface wetting possible that otherwise would notoccur.

Dispersants are generally suitable for stabilizing solid particles inbinders, lacquers, pigment pastes, plastics and plastic mixtures,adhesives and sealants, for reducing the viscosity of appropriatesystems, and for improving flow properties. Dispersion stabilizers areused for stabilizing previously produced dispersions.

Large mechanical forces are needed for introducing solids into liquidmedia. It is customary to introduce dispersants to reduce the dispersionforces and to minimize the total energy input into the system fordeflocculating the solid particles and thus also keeping the dispersiontime as low as possible. Such dispersants are surface-active substancesthat are anionic, cationic and/or neutral in structure. Small quantitiesof these substances are either applied directly to the solid or added tothe dispersion medium. It should be noted that even after completedeflocculation of the solids agglomerates into primary particles(following the dispersion process), reagglomeration may occur, partiallyor completely undoing the effort of dispersion. As a result ofinsufficient dispersion or reagglomeration, unwanted effects frequentlyoccur, such as viscosity increases in liquid systems, color drift andloss of luster in lacquers or coatings and reduction of the mechanicalstability and material homogeneity in plastics.

In practice, various types of compounds come under consideration aswetting agents and dispersants. This is especially due to the fact thata large number of different systems exists, which are based inparticular on various binders in combination with different particles tobe dispersed, such as pigments, fillers and fibers.

EP-B-1 080 128 relates to special amino groups andpoly(oxyalkylenecarbonyl) chain-containing dispersants which areproduced through a Michael addition reaction in which a startingcompound is bound to an ethylenically unsaturated group of a “MichaelAcceptor” containing a poly(oxyalkylenecarbonyl) chain.

To be sure, dispersants of this type are fundamentally suitable for thedispersion of solids, but they have only a limited universality,especially in regard to the solids to be dispersed, which restrictstheir suitability for different dispersion tasks.

The present invention was thus based on the task of supplying a processfor preparing high-quality dispersant additives that are as nearlyuniversally usable as possible.

The solution to this problem is a method for preparing an amine adductin which the reaction of a polyamine component (A), a polyestercomponent (B) and a hydrocarbon component (C) in weight ratios of

-   -   (A):(B)=1:1000 to 1:1    -   (A):(C)=1:100 to 100:1 and    -   (B):(C)=2:1 to 50:1    -   is performed in that according to reaction variants        -   i) first a reaction intermediate (A-B) is produced from the            polyamine component (A) and the polyester component (B) and            this is then reacted with the hydrocarbon component (C) or    -   according to reaction variant        -   ii) first a reaction intermediate (A-C) is formed from the            polyamine component (A) and the hydrocarbon component (C)            and this is subsequently reacted with the polyester            component (B) or    -   according to reaction variant        -   iii) first the polyamine component (A) is reacted            simultaneously with the polyester component (B) and the            hydrocarbon component (C),    -   wherein the polyamine component (A) is present in the form of        organic polyamine compounds (A′), which in each case have at        least three amino groups (A′+) selected from primary and        secondary amino groups in each case reactive with both the        polyester component (B) and the hydrocarbon component (C),    -   the polyester component (B) is present in the form of polyester        compounds (B′), which in each case contain no primary amino        groups and which in each case no secondary amino groups, in each        case have at least three ester groups, and in each case contain        a coupling group (B′+) present as a carboxyl group or carboxylic        acid anhydride group, reactive with primary and/or secondary        amino groups, and        -   the hydrocarbon component (C) is present in the form of            branched or unbranched, saturated or unsaturated hydrocarbon            compounds (C′) each having a linking group (C′+), in each            case having no primary amino groups, in each case having no            secondary amino groups, in each case having no carboxyl            groups and no carboxylic acid anhydride groups, and in each            case having an overall ratio of carbon atoms to hetero atoms            selected from the group of elements O, N, P, S, [and] Si of            at least 2:1, wherein the linking groups (C′+) in each case            have the characteristic of reacting with primary amino            groups with formation of secondary amino groups and/or with            secondary amino groups with formation of tertiary amino            groups, and also in each case are present    -   in the form of an epoxy function of general formula (I)

-   -   -   with        -   R¹, R², and R³ in each case the same or different and in            each case independently represented by H and/or by a            saturated, branched or unbranched C₁-C₁₂ hydrocarbon moiety.

    -   wherein the amine adduct is obtained in solid form at room        temperature and has a melting range of 30 to 200° C.

The polyamine component (A) represents the totality of all polyaminecompounds (A′) (which may be the same or different), wherein thereactive amino groups (A′+) (which may be the same or different) in eachcase are molecular components of the polyamine compounds (A′).

Correspondingly, the polyester component (B) consists of the totality ofall hydrocarbon compounds (B′) (which may be the same or different),wherein the coupling groups (B′+) in each case are molecularconstituents of the polyester compounds.

The hydrocarbon group (C) represents the totality of all hydrocarboncompounds (C′) (which may be the same or different), wherein the linkinggroups (C′+) in each case are molecular constituents of the hydrocarboncompounds (C′).

According to reaction variant i), at least initially (at the beginningof the reaction), but often up to complete reaction of (B), (B) isreacted with (A) with formation of (A-B), specifically without (C)simultaneously reacting with (A) (or with the secondary product of (A)).Then (A-B) is reacted with (C), wherein this can optionally also takeplace in the presence of (B) (simultaneous reaction of (A-B with (B) and(C)).

According to reaction variant ii), at least initially (at the beginningof the reaction), but often up to complete reaction of (C), (C) isreacted with (A) with formation of (A-C), specifically without (b)simultaneously reacting with (A) (or with the secondary product of (A)).Then (A-C) is reacted with (B), wherein this may also optionally takeplace in the presence of (C) (simultaneous reaction of (A-C) with (B)and (C)).

According to reaction variant iii), at least initially (at the beginningof the reaction), but often over the entire reaction period, (A) isreacted simultaneously with (BO and (C).

The wording “same or different” is intended to mean that the respectivemoiety, substituent or constituent of the molecule can vary both withina (macro)molecule and also between different (macro)-molecular speciesof the same general formula.

The relevant amine adduct is normally present as a (an industrial) rawproduct, which can optionally contain solvents, byproducts and unreactedstarting components.

It should be emphasized that the relevant amine adducts according to theinvention exhibit a good dispersing effect toward broad spectrum ofsolids to be dispersed. This is manifested, among other things, in thefact that not only particularly solids with basic surfaces, but alsosolids with neutral and even acidic surfaces can be dispersedeffectively.

The relevant amine adducts are therefore of particularly high qualityand are universally usable as wetting and dispersing agents. It can alsobe stated that the amine adducts can be used successfully in both polarand nonpolar binder systems, and in this case exhibit excellenttolerability as wetting and dispersion agents and also as dispersionstabilizers. This guarantees successful use in combination with a greatvariety of binders and coating materials. In addition, the amine adductsaccording to the invention permit flocculation-free miscibility ofpastes, especially pigment pastes, and the binders produced with thesepastes. Furthermore the amine adducts are suitable as dispersionstabilizers, especially as emulsion stabilizers. Through the use of theamine adducts, the viscosity of the ground material introduced duringthe dispersion is markedly reduced, and in this way it enables theproduction of formulations which have a high solids content. In thisway, the fraction of (volatile) solvents can be reduced to provide forbetter environmental safety. In summary, it can be said that the amineadducts n, while providing good stabilization of pigments or fillers,can lower the viscosity of the ground material in the lacquers, pastesor plastics formulations produced to such an extent that processing at ahigh degree of filling can be achieved without having a negative effecton the durability of the hardened lacquers. It is also essential thatthe amine adducts according to the invention, used as additives, shouldbe highly effective even at low concentrations. Furthermore, the goodshelf life of the amine adducts should be mentioned. Finally it shouldbe mentioned that the amine adducts can be produced economically and arebased on widely available starting materials.

In a preferred embodiment of the invention, the polyester component (B)and the hydrocarbon component (C) under the reaction conditions of thereaction do not react with one another. This is also desired, as a rule,for all species corresponding to (B) and (C).

The polyester component (B) and the hydrocarbon component (C), however,can optionally react to a slight extent under the reaction conditions ofthe reaction if these starting components are simultaneously present inthe reaction mixture. This is known to the person skilled in the art,since the epoxy function intended for linking the hydrocarbon component(C) is markedly reactive, so that in practice secondary reactions maketake place (although they are unwanted and occur only to a slightextent. By suitably selecting the reaction conditions, the secondaryreactions mentioned can be suppressed to a level where they do notinterfere or completely.

According to a special reaction variant iv) the polyamine component (A),the polyester component (B) and the hydrocarbon component (C) can bereacted, with the specification, in quantitative ratios varying overtime, that at least the first time segment of the reaction takes placeaccording to one of reaction variants i) to iii). Reaction variant iv)thus takes place at least (in a first time segment) according to one ofthe reaction variants i) to iii) and is thus to be regarded as a specialcase of one of the reaction variants i) to iii). The reaction of (C) and(C) takes place, according to reaction variant iv), in quantitativeratios that vary over time. For example, the reaction takes place in atleast three steps, in that (A) or appropriate secondary products of (A)are reacted in successive time segments in each case with either B or C.

In a preferred embodiment of the invention, the reaction of (A), (B) and(C) is performed in weight ratios of

-   -   (A):(B)=1:100 to 1:4, preferably (A):(B)=1:25 to 1:7 and    -   (A):(C)=1:10 to 10:1, preferably (A):(C)=1.2 to 2:1.

A low fraction of (A) often results in low adsorption on the surfaces ofsolids, while a high fraction of (A) can often mean poor solubility anddifficult handling.

Regarding the polyamine component (A):

Examples of suitable polyamine compounds (A′) of the polyamine component(A) are aliphatic linear polyamines, such as diethylenetriamine (DETA),triethylenetetramine (TETA), tetraethylenepentamine (TEPA),pentaethylenehexamine, hexaethyleneheptamine and higher homologs, higherlinear condensates with the general formula of NH₂—(C₂H₄NH), —C₂H₄—NH₂with n>5, dipropylenetriamine, (3-(2-aminoethyl)aminopropylamine,N,N-bis(3-aminopropyl)methylamine, tetramethyliminobispropylamine,N,N-dimethyldipropylenetriamine, bis-(3-dimethylaminopropyl)amine andN,N′-bis(3-aminopropyl)-ethylenediamine.

Frequently, the polyamine component (A) is present in the form oforganic polyamine compounds (A′), which in each contain at least 2,preferably in each case 6-600, tertiary amino groups.

Tertiary amino groups typically cause good adsorption on surfaces ofsolids and a slight tendency to secondary reactions. In addition, thetertiary amino groups enable high-molecular-weight structures, whereasthe viscosity remains relatively low.

Typically, branched aliphatic polyamines, especially poly(C₂-C₄)-alkyleneamines, with primary, secondary and tertiary aminogroups are used. Particularly are the aziridine homopolymers also knownunder the name of polyethyleneimines, for example the Lupasol® typesfrom BASF or the Epormin® types from Nippon Shokubai. These are producedby known methods, e.g., by the polymerization of ethyleneimine.

Usually in the organic polyamine compounds (A′) the molar ratio ofprimary to secondary amino groups in each case amounts to 1:1 to 1:5 andthe molar ratio of primary to tertiary amino groups in each case amountsto 3:1 to 1:3.

Primary amines are more reactive than secondary amines, so that a smallfraction of primary amines can mean a low reactivity toward the build-upreaction.

As a rule, the totality of the organic polyamine compounds (A′) have aweight-average molecular weight of 250 to 200,000, preferably 600 to40,000, and particularly preferably 800 to 10,000 g/mol.

A low molecular weight often causes weak adsorption on the surfaces ofsolids, while a high molecular weight can be problematic in terms ofmanageability and solubility.

If nothing is said to the contrary at the location in question,statements regarding the weight-average molecular weight in connectionwith the present invention generally are based on the light-scatteringmeasurement method.

In addition to unmodified polyamines, partially modified polyamines, asdescribed in EP-893 155, may also be used. These modified polyamines,for example, may relate to condensates of the above-described polyamineswith carboxylic acids such as stearic acid, oleic acid or tall oil fattyacid bound to the polyamine by way of amide groups. It is also possibleto react parts of the primary or secondary polyamine withmonoisocyanates such as stearylisocyanate and/or polyisocyanates.

An additional suitable class of polyamines is homo-, co- or blockcopolymers with at least three primary or secondary amino groups, whichcan either be produced by free moiety or ionic polymerization, or formedby means of a polymer-analogous reaction on a preformed polymer orintroduced into such [a polymer]. Homo-, co- or block copolymers of thistype have a weight-average molecular weight of up to 1,000,000 g/mol,preferably form 600 to 200,000 g/mol. The polyamines in question can beused individually or in a mixture.

Regarding the polyester component (B):

Examples of suitable polyester compounds (B′) of the polyester component(B) are compounds produced by reacting dicarboxylic acids and theiresterifiable derivatives such as anhydrides, acid chlorides or dialkylesters, such as dimethyl esters or diethyl esters, by reacting withdiols and monofunctional carboxylic acids. If necessary, the formationof dihydroxypolyesters can be suppressed by the use of correspondingstoichiometric quantities of monofunctional carboxylic acids. Theesterification can be performed in bulk or by azeotropic esterificationin the presence of an entrainment agent. Such condensation reactions areperformed, for example, at temperatures from about 50° C. to 250° C.Examples of dicarboxylic acids that can be used in this way are succinicacid, maleic acid, fumaric acid, glutaric acid, adipic acid, sebacicacid, pimelic acid, phthalic acid or dimerized fatty acids and theirisomers as well as their hydrogenation products. Examples of diols thatcan be used in this way are: ethylene glycol, 1,2-propanediol,1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol,cis-1,2-cyclohexanedimethanol, trans-1,2-cyclohexanedimethanol, andpolyglycols based on ethylene glycol and/or propylene glycol.Corresponding monocarboxylic acids used as starting componentspreferably have 1 to 42, especially 4 to 18, preferably 8 to 14 carbonatoms and can be saturated or unsaturated, aliphatic or aromatic,linear, branched and/or cyclic. Examples of corresponding, suitablemonocarboxylic acids are stearic acid, isostearic acid, oleic acid,lauric acid and benzoic acid. Additional suitable acids are the tertiarymonocarboxylic acids, also known as Koch acids, such as2,2-dimethylpentanoic acid, tert-nonanoic acid and neodecanoic acid.Koch acids of this type are also known as commercial products under thenames of Versatic® acids (Shell), Neo-acids (Exxon) or CeKanoic acids(Kuhlmann). The Versatic® acids are named according to the total numberof carbon atoms that the molecule contains. Suitable examples are theVersatic® acids 5, 6 9, 10, 913 [and]1019.

The polyester component (B) is usually present in the form of polyestercompounds (B′), each of which contains at least 5, preferably in eachcase 6 to 70, ester groups.

Ester groups typically improve the solubility.

According to special embodiments of the invention, the polyestercompounds (B′) additionally contain ether groups.

Each of the polyester compounds (B′) preferably contains at least onereactive coupling group (B′+), preferably reactive, wherein each of thepolyester compounds (B′) preferably contains no additional functionalgroups that react with the polyamine component (A) during the reaction.

Monofunctionality is desired to avoid cross-linking, which usually leadsto deterioration of solubility, reduced compatibility, excessiveviscosities or inadequate compatibility.

Often at least 50% by weight, preferably 70 to 100% by weight, of thepolyester compounds (B′) used are present in the form of linear,monocarboxy-functional caprolactone polyesters, which each preferablyhas a weight-average molecular weight of 500 to 10,000, preferably of800 to 8,000.

Weight-average molecular weights of less than 500 or more than 10,000often impair the universal compatibility.

Particularly suitable polyesters are those that can be obtained bypolycondensation of one or more, optionally alkyl-substituted,hydroxycarboxylic acids such as ricinoleic acid or 12-hydroxystearicacid and/or ring-opening polymerization of the corresponding lactones,such as propiolactone, valerolactone, and caprolactone. The lactonepolymerization is performed using known methods, initiated with, forexample, p-toluenesulfonic acid or dibutyltin dilaurate, at temperaturesfrom about 50° C. to 200° C. Particularly preferred are polyesters onthe basis of ε-caprolactone, optionally in combination withδ-valerolactone.

Regarding the hydrocarbon component (C):

Preferably the hydrocarbon compounds (C′) of the hydrocarbon component(C) each have exactly one linking group (C′+) and preferably do notcontain any additional functional groups that react with the polyaminecomponent (A) during the reaction.

The monofunctionality reduces the tendency toward cross-linking, whichgenerally leads to poor solubility, poor compatibility and excessiveviscosities. According to the invention, all of the linking groups (C′+)are present respectively in the form of epoxy functions of generalformula (I).

Preferably in the general formula (I) for the linking groups (C′+), R¹,R² and R³ are each represented by H.

Suitable epoxy-functional substances are, for example, aliphatic,cycloaliphatic and/or aromatic glycidyl ethers, for example C₁-C₂₀alkylglycidyl ethers, phenylglycidyl ethers, cresyl glycidyl ethers,naphthyl glycidyl ethers, butylglycidyl ethers, p-tert-phenyl glycidylethers, 2-ethylhexyl glycidyl ethers, C₁₂-C₁₄ glycidyl ethers, allylglycidyl ethers, 2,3-epoxypropylneodecanoate (Cardura® E10, ResolutionPerformance Products) or bisphenol A-based epoxides (Epikote types).Monofunctional epoxides are preferred. A secondary hydroxy group formsduring the reaction with the epoxides, and a secondary or tertiary aminogroup on the nitrogen atom involved in the reaction.

Typically, the hydrocarbon compounds (C′) of the hydrocarbon component(C) each contains a total of 6 to 70 carbon atoms.

A number of less than 6 carbon atoms often results in excessivepolarity, while more than 70 carbon atoms usually impairs the universalcompatibility.

In a special embodiment of the invention, the hydrocarbon component (C)contains at least 30% by weight, preferably 50 to 100% by weight, ofunsaturated C₆-C₅₀ hydrocarbon compounds (C′), which in each casecontains at least one aryl and/or alkylaryl moiety.

Aromatic groups frequently give the products a particularly goodadsorption capability toward many particle surfaces.

According to a particular variant of the invention, the hydrocarboncomponent (C) contains at least 30% by weight, preferably 50 to 100% byweight, of unsaturated C₁₀-C₇₀ hydrocarbon compounds (C′), which in eachcase contains at least one branched alkyl and/or one branched alkenylmoiety.

Branched groups often result in better solubility and generally promoteuniversal compatibility.

Frequently, the hydrocarbon compounds (C′) of the hydrocarbon component(C) in each case contain a total of 6 to 24 carbon atoms andadditionally a maximum of three hetero atoms from the group of elementsO, N, P, S, Si. According to the invention, other hetero atoms (asidefrom the last-mentioned ones) are preferably not present (in (C′)).

Preferably, components (A), (B) and (C) are used respectively instoichiometric ratios such that altogether at least 50 mol %, preferably70 to 100 mol % of the totality of the reactive amino groups (A′+) ofthe polyamine compounds (A′) used are reacted with the polyestercompounds (B′) and/or with the hydrocarbon compounds (C′).

Corresponding conversion rates less than 50% usually signify productswith a large number of reactive amino groups, which have a tendencytoward undesirable secondary reactions. As a result, productdiscolorations, reduced pot lives and less advantageous storagestabilities are encountered.

A partial quantity (preferably less than 50 mole-%, particularly lessthan 30 mole-%) of the reactive amino groups (A′+) of the polyaminecompounds (A′) can (among other things) be made to react with carbonatecompounds (D′) of a carbonate component (D) and/or with carboxylic acidcompounds (F′) of a carboxylic acid component (F). Compounds belongingto the groups (D) or (F) by definition are not species that can beassigned to (A), (B) or (C).

Components (D) and (F) in each case may further increase theuniversality.

By reacting a partial quantity of the primary and secondary amino groupsof the polyamines (A) with component (D) and/or component (F),additional modifications are made possible to optimize furtheradaptations to special systems.

Suitable carbonates in this connection are aliphatic, cycloaliphaticand/or aromatic carboxylic acid esters, such as dialkyl carbonates,e.g., dimethyl carbonate, diethyl carbonate or diphenyl carbonate,catechol carbonate or cyclic alkylene carbonates. Particularly suitableare cyclic alkylene carbonates with 5- or 6-membered rings, which mayoptionally be substituted. Suitable substituents are aliphatic,cycloaliphatic and/or aromatic groups with up to 30 carbon atoms.Examples of corresponding suitable alkylene carbonates are ethylenecarbonate, propylene carbonate, glycerol carbonate, trimethylenecarbonate, 4-methyltrimethylene carbonate, 5-methyltrimethylenecarbonate, 5,5-dimethyl trimethylene carbonate, 5,5-diethyl trimethylenecarbonate or 5-methyl-5-propyltrimethylene carbonate.

Suitable carboxylic acids and carboxylic acid anhydrides are aliphatic,cycloaliphatic and/or aromatic carboxylic acids and the anhydridesthereof, such as acetic acid, propionic acid, benzoic acid, nitrobenzoicacid, acetic anhydride, succinic anhydride, maleic anhydride, phthalicanhydride, tetrahydrophthalic anhydride, alkyltetrahydrophthalicanhydride, hexahydrophthalic anhydride, alkyl-hexahydrophthalicanhydride, trimellitic anhydride, alkenyl- and/or alkyl-succinicanhydride with preferably 1 to 20 carbon atoms in the alkenyl or alkylchains.

According to the invention, the amine adduct is always obtained in solidform at room temperature, wherein (B) to (C) is reacted in a weightratio of 2:1 to 50:1 and the amine adduct has a melting range of 30 to200° C. Weight ratios outside of the aforementioned range usuallyinterfere with the universality, while other melting ranges alsofrequently make handling more difficult. However, the amine adduct mayalso be obtained in liquid form and only achieve the solid form afterclean-up (invention variant 2).

This variant 2 has the following drawbacks compared to invention variant1: the removal of the solvent used is an extra working step, which isespecially financially disadvantageous in (large) industrial scaleoperations because of high costs for energy, time and equipment. As arule, despite this additional industrial effort, it is not possible toremove the solvent completely. The result is then a product behaviorthat is poorly suited or unsuitable for low-VOC or VOC-freeapplications. For use in solvent-containing applications as well, it isusually advantageous if such solvent-free additives are used, since as aresult the “entrainment” of undesirable “foreign solvents” is avoided.In other words, solvent-free additives offer the user optimal freedomwith regard to solvent selection. Especially in the case ofenvironmentally safe solvent recovery systems, “foreign solvents”usually cause technical problems.

According to the invention, the reaction of the polyamine component (A),the polyester component (B) and the hydrocarbon component (C) takesplace in that for each unit weight of polyester component (B), a maximumof 0.8, preferably a maximum of 0.2 units by weight of other componentsare present, which do not belong to any of the components (A), (B) or(C) (and also not to the pure reaction product). As a result of suchlimitations on use of the other components especially solvent, the amineadduct can already be obtained in solid form without clean-up. In atypical embodiment of the invention, the reaction of the polyaminecomponent (A), the polyester component (B) and the hydrocarbon component(C) takes place in the absence of organic solvents. This is preferredaccording to the invention.

However, the solid form permits use for applications for whichexclusively solid additives can be used. For example, applications forthermoplastic processing may be mentioned. Additional applications to bementioned are powder lacquer applications, toner applications andapplications for solid pigment preparations.

The manufacturing of the compounds according to the invention, dependingon their viscosity, may be performed in bulk or in the presence ofsuitable solvents, solvent mixtures or other suitable carrier media.Preparation in bulk is preferred. For example, if the products are to beused where the presence of volatile organic compounds (VOC) is notdesired, the formulation should be solvent-free insofar as possible orshould be present in appropriate carrier materials that can beconsidered VOC-free.

Also relevant is the amine adduct that can be produced by one of theabove-mentioned methods.

The relevant amine adduct is preferably suitable as a wetting agent anddispersing agent, especially for lacquer and plastics applications.

Typically, the relevant amine adduct has a weight-average molecularweight of 5,000 to 100,000.

The relevant amine adduct frequently has a spherical (micro)structure,which in each case contains a hyperbranched polyalkyleneimine core, tothe outer shell of which polyester groups and hydrocarbon groups arebound.

The use of the above-described amine adduct or the amine adduct that canbe produced according to the above-described process as an additive, incoatings, especially in lacquers, in plastics, in pigment pastes, insealants, in cosmetics, in ceramics, in adhesives, in casting compounds,in pigment-containing compounds of flat-screen technology, in fillingcompounds, in printing inks and in inks, preferably in lacquers shouldalso be mentioned.

In this application, the amine adduct is preferably used as a wettingand dispersing agent.

The present invention also relates to a mixture of solids containingparticles and/or fibers that have been treated with the above-describedamine adduct.

Finally, also relevant is a lacquer and/or plastic containing theabove-described amine adduct.

The relevant amine adducts may be used, for example, as aluminumpassivators, dispersants, dispersion stabilizers or wetting agents andcan be employed for example in pigmented and/or filler-containingproducts, for example pigment concentrates or pastes, coatingcompositions, sealants, plastics, ceramics, cosmetics, adhesives,potting compounds, filling compounds, printing inks and/or inks.Preferred are pigment concentrates that can be mixed with correspondinglacquer forming systems, yielding pigmented lacquers.

For example, these can be used in the manufacturing or processing oflacquers, printing inks, inks, for example for ink-jet printing, papercoatings, leather and textile dyes, pastes, pigment concentrates,ceramics, adhesives and sealants, potting compounds, plastics andcosmetic preparations, especially if these contain solids such aspigments and/or fillers. These can also be used in the manufacturing orprocessing of molding compositions on the basis of synthetic,semisynthetic or natural macromolecular substances, such as polyvinylchloride, saturated or unsaturated polyesters, polyurethanes,polystyrenes, polyacrylates, polyamides, epoxy resins, [and]polyolefinssuch as polyethylene or polypropylene. For example, the compounds may beused for producing potting compounds, casting compounds, PVC plastisols,gelcoats, polymer concrete, circuit boards, industrial lacquers, woodand furniture lacquers, vehicle lacquers, ship paints, anticorrosionpaints, can-coatings and coil-coatings or art paints and engineeringpaints.

The relevant amine adducts can not only be used in lacquer applicationsystems for pigmented lacquers.

It is also possible to use them in a broad range of formulations orproducts, such as resins, oils, fats, lubricants, rubber materials,sealants, printing inks, inks, adhesives, waxes or coating materialcompositions. The concentrates can also be used in formulations that maybe manufactured in the body care industry or for electrical uses in theelectronics industry, in the shipbuilding industry, in medicalapplications, in the construction industry or in the automotiveindustry. Examples include electronic paper, such as the display one-books, the encapsulation of microelectronic chips and circuit boards,underwater ship hull coatings, such as anti-fouling coatings, siliconetubing or lubricants for brake components.

The relevant amine adducts can also be used advantageously in producingcolor filters for liquid crystal displays, liquid crystal screens, colorresolution devices, sensors, plasma screens, displays based on SED(Surface conduction Electron Emitter Display) and for MLCC (Multi LayerCeramic Compounds). MLCC technology is used in manufacturing microchipsand circuit boards.

Application in cosmetic preparations can serve, for example, formanufacturing cosmetic preparations such as make-up, powder, lipstick,hair colorings, creams, nail polish and sunscreen preparations. Thesecan exist in their usual forms, for example as W/O or O/W emulsions,solutions, gels, creams, lotions or sprays. The compounds can be usedadvantageously in dispersions for producing these preparations. Thesecan contain carrier media commonly used for such purposes in cosmetics,such as water, castor oil or silicone oil and solids, such as organicand inorganic pigments, such as titanium dioxide or iron oxide.

Also to be mentioned are the application areas of NIP (non-impactprinting), InkJet (on paper, film, ceramic, artificial and natural fibermaterials), dispersion of ceramics (aqueous or waterless),[and]dispersion in potting compounds. The amine adducts can also be usedas such, i.e., without first being incorporated in a correspondingconcentrate, in the aforementioned formulations and application areas.

Typically the product containing the amine adduct and pigment- and/orfiller-containing product is a lacquer, or a pigment concentrate forcoating compositions. Ultimately, however, the use of the amine adductsin any pigment-containing and/or filler-containing products whatsoeveris possible.

In particular, the pigment concentrates are compositions which, inaddition to the relevant amine adducts, contain, for example, organicsolvents and at least one pigment. In particular, these contain no oronly small quantities of organic polymers as binder. Such known bindersare advantageously present in the corresponding lacquer applicationsystems and will be described in the following.

Organic solvents used, in particular, are the typical organic solvents,familiar to the person skilled in the art, used in the area of thelacquer and paint industry, such as aliphatic solvents, cycloaliphaticsolvents, aromatic solvents, such as toluene, xylene, solvent naphtha,ethers, esters and/or ketones, for example butylglycol, butyldiglycol,butyl acetate, methylisobutyl ketone, methylethyl ketone and/ordissolvers such as methoxypropyl acetate, [and]diacetone alcohol.

Pigments used may include the pigments known to the person skilled inthe art. Examples of pigments are mono-, di-, tri- and polyazo pigments,oxazine, dioxazine, [and]thiazine pigments; diketo-pyrrolo-pyrroles,phthalocyanines, ultramarine and other metal complex pigments, indigoidpigments, diphenylmethane pigments, triarylmethane pigments, xanthenepigments, acridine pigments, quinacridone pigments, methine pigments,anthraquinone, pyranthrone, [and]perylene pigments and other polycycliccarbonyl pigments, inorganic pigments, such as carbon black pigmentsand/or pigments based on lamp black, graphite, zinc, titanium dioxide,zinc oxide, zinc sulfide, zing phosphate, barium sulfate, lithopone,iron oxide, ultramarine, manganese phosphate, cobalt aluminate, cobaltstannate, cobalt zincate, antimony oxide, antimony sulfide, chromiumoxide, zinc chromate, mixed metal oxides based on nickel, bismuth,vanadium, molybdenum, cadmium, titanium, zinc, manganese, cobalt, iron,chromium, antimony, magnesium, [and]aluminum (for example nickeltitanium yellow, bismuth-vanadate-molybdate yellow or chromium-titaniumyellow), magnetic pigments based on pure iron, iron oxides and chromiumoxides or mixed oxides, metal effect pigments made of aluminum, zinc,copper or brass and pearlescent pigments or fluorescent andphosphorescent luminescent pigments. Additional examples are nano-scaleorganic or inorganic solids with particle sizes of less than 100 nm inat least one dimension, such as certain lamp black types or otherallotropic forms of carbon, for example single-wall CNTs, multi-wallCNTs and graphene. The determination of the particle size is performed,for example, by transmission electron microscopy, analyticalultracentrifugation or light scattering methods. Also to be mentionedare particles consisting of a metal or semimetal oxide or hydroxide, aswell as particles consisting of mixed metal and/or semimetal oxides orhydroxides. For example, the oxides and/or oxide-hydroxides of aluminum,silicon, zinc, titanium, etc., can be used for producing such extremelyfine particulate solids. The manufacturing process of these oxidic andhydroxidic or oxyhydroxidic particles can take place through a greatvariety of methods such as ion exchange processes, plasma processes,sol-gel methods, precipitation, size reduction (for example bygrinding), or flame hydrolysis. All of the aforementioned pigments canexist in surface-modified form and have basic, acidic or neutral groupson the surface.

If the respective products, especially the coating compositions, containfillers, they are, for example, fillers known to the person skilled inthe art. Examples of powdered and fibrous fillers are, for example,those that are made up of powdered or fibrous particles of aluminumoxide, aluminum hydroxide, silicon dioxide, diatomaceous earth,siliceous earth, quartz, silica gel, talc, kaolin, mica, perlite,feldspar, slate flour, calcium sulfate, barium sulfate, calciumcarbonate, calcite, dolomite, glass or carbon. The fibers used may beorganic or inorganic in nature and may also be used as reinforcingagents. Additional examples of pigments or fillers can be found, forexample, in U.S. Pat. No. 4,795,796. Flame retardants such as aluminumor magnesium hydroxide and delustering agents, such as silicas, may alsobe dispersed and stabilized particularly well by the relevant wettingand dispersing agents, insofar as the compounds according to theinvention are not already used in the customary additive quantities forthis purpose.

The relevant amine adducts are also especially suitable for producingsolids concentrates, such as pigment concentrates. For this purpose, theamine adducts according to the invention are provided in a carriermedium such as organic solvents, plasticizers and/or water, and thesolids to be dispersed are added under agitation. In addition, theseconcentrates may contain binders and/or other auxiliaries. With theamine adducts according to the invention, however, it is possible inparticular to produce stable, binder-free pigment concentrates. It isalso possible to produce free-flowing solid concentrates from pigmentpress cakes using the amine adducts according to the invention. In thisprocess, the compound according to the invention is mixed into the presscake, which may also contain organic solvent, plasticizer and/or water,and the mixture thus obtained is dispersed. The solid concentratesproduced in various ways can then be incorporated into differentsubstrates, such as alkyd resins, polyester resins, acrylate resins,polyurethane resins or epoxy resins. However, pigments may also bedispersed directly into the amine adducts according to the inventionwithout solvents and are then especially suitable for pigmentation ofthermoplastic and duroplastic plastic formulations.

Depending on the application area, the relevant amine adducts are usedin quantities such that in the product, which is of ultimate interestfor further application, a fraction of the wetting and dispersing agentaccording to the invention of 0.01 to 10 wt. %, based on the totalquantity of the respective product, is present. Higher fractions arealso possible.

Based on the solid, for example the pigment, to be dispersed, thewetting agent and dispersant according to the invention is used in aquantity of preferably 0.5 to 100% by weight. If difficult to dispersesolids are used, the quantity of the wetting agent and dispersantaccording to the invention definitely can be greater. The quantity ofdispersant generally depends on the surface area of the dispersiblesubstance that is to be covered. The pigment involved, for example, mayalso be significant.

In general, it can be said that less dispersant is usually required fordispersing inorganic pigments than for organic pigments, since thelatter usually have a higher specific surface and consequently a largeramount of dispersant is necessary. Typical addition rates of the wettingagents and dispersants for inorganic pigments are, for example, 1 to 20%by weight, and for organic pigments, 10 to 50% by weight, in each casebased on the solid to be dispersed, especially the pigment. In the caseof very fine-particulate pigments (for example some lampblacks),addition rates of 30 to 90% or more are necessary. Criteria for adequatepigment stabilization may be, for example, luster and transparency ofthe coating composition or the degree of floating. The dispersion of thesolids can take place as an individual milling or as a mixed millingwith several pigments simultaneously; as a rule, the best results areachieved with individual millings. When mixtures of various solids areused, increased agglomeration in the liquid phase may occur because ofopposite charges on the solid surfaces. In these cases, when the amineadducts according to the invention are used, the same type of charge,usually a positive one, on all particles can often be achieved, and thusinstabilities due to charge differences can be avoided. The dispersantsachieve their optimal effect when added to the ground material,especially if at first the solid to be dispersed is mixed only with theadditive and optionally solvents ((“premix”), since in that case theadditive preferentially adsorbs on the surface of the solid withouthaving to compete with the binder polymers. In practice, however, thisprocedure is only necessary in exceptional cases. If necessary the amineadducts according to the invention may also be added subsequently (asso-called “post-additives”), for example to solve floating orflocculation problems in a batch that has already been made into alacquer. As a rule, higher additive addition rates are necessary in thiscase.

The products, especially the coating compositions or lacquers in whichthe amine adducts according to the invention are ultimately intended toproduce their effects, can also contain an organic polymer as thebinder. Such binders are known to the person skilled in the art. This atleast one binder can, for example, be introduced via a lacquer systemwhich is mixed for example with a pigment concentrate containing theamine adducts according to the invention, so that the product underconsideration is a pigment lacquer. Also possible are other pigmentedand/or solids-containing products, for example plastics, sealants andadditional products based on an organic polymer matrix known to theperson skilled in the art. A product may be regarded as a system thatcontains a polymeric resin or organic polymer as binder and consequentlyis capable of forming such an organic, polymeric matrix (for example apigment concentrate) by simply mixing with a component containing abinder. Examples of products that may be used, possibly but notexclusively known to the person skilled in the art, are alkyd resins,polyester resins, acrylate resins, polyurethane resins, cellulosenitrates, cellulose acetobutyrates, melamines, chlorinated rubbersand/or epoxy resins. Examples of water-based coatings are cathodic oranodic electrodip lacquer finishes, e.g., for auto bodies. Furtherexamples are polishes, silicate paints, dispersion paints, water-basedlacquers based on water-thinnable alkyds, alkyd emulsions, hybridsystems, 2-component systems, polyurethane and acrylate dispersions.

Both 1-component systems and 2-component systems are possible. In thelatter case, polyisocyanates, melamine resins and/or polyamide resinsare present as the typical crosslinking agents, familiar to the personskilled in the art, in a second component. Product systems, especiallycoating compositions, which contain an acrylate resin as a binder arepreferred. An additional variant involves a 2-component (2C) coatingcomposition or a 2C lacquer, which contains an epoxy resin in the bindercomponent and a polyamide resin in the cross-linker component.

The coating compositions preferred as products can be water-based orsolvent-based. Water-based means that the coating composition chieflycontains water as the solvent. In particular, in a water-based coatingcomposition, no more than 10 wt. % organic solvent, based on the totalquantity of solvents, are present in the coating composition. Asolvent-based coating composition is one that contains no more than 5%by weight of water, preferably no more than 2% by weight of water, basedon the total quantity of solvents.

Additional product components to consider as examples arephotoinitiators, defoamers, wetting agents, film-forming aids such ascellulose derivatives (for example cellulose nitrate, cellulose acetate,cellulose acetobutyrate), reactive diluents, leveling agents,dispersants, and/or rheology-controlling additives.

The production of the pigment concentrates and coating compositionpreferred as products is performed using the method customary for theperson skilled in the art. The known methods are used, for examplestepwise addition under agitation and mixing the components of thecoating composition in the usual mixing units, such as agitator vesselsor dissolvers.

Coatings or lacquer layers can be produced using the preferred pigmentconcentrates and coating compositions. The coating is prepared usingapplication techniques commonly employed by the person skilled in theart on a substrate, followed by hardening.

The application is performed, for example, by the familiar spraying,squirting, painting, rolling, casting, soaking and/or dipping methods.Following application of the coating composition to a substrate, thehardening or drying is performed by usual methods. For example, theapplied coating composition can be hardened by physical drying,thermally and/or actinic radiation (radiation-hardening), preferably UVradiation as well as electron bombardment. Thermal hardening can takeplace for example in the range from about 10° C. to about 400° C.,depending on the type of coating composition and/or substrate. Thehardening time is also dependent in the individual case, for example, onthe type of hardening process (thermal or actinic), the type of coatingcomposition used and/or the substrates. The substrate may be moving orstill.

In addition to the above-described use as a dispersant and/or coatingagent for powdered and fibrous solids, the relevant amine adducts canalso be used as viscosity reducers and compatibility enhancers insynthetic resins. Examples of such synthetic resins are the so-called“sheet molding compounds” (SMC) and “bulk molding compounds” (BMC),which consist of unsaturated polyester resins with high filler and fibercontents. Their manufacture and processing is described, for example, inU.S. Pat. No. 4,777,195. One problem with SMC and BMC synthetic resinmixtures consists of the fact that often polystyrene (PS) is added tothe formula to reduce shrinking while processing. PS is not compatiblewith the unsaturated polyester resins used, and separation of thecomponents occurs. When PS-filled SMC or BMC mixtures are used, theamine adducts according to the invention, because of their gooddispersion qualities, can also bring about compatibility between PS andunsaturated polyester resin, increasing the shelf life and processingreliability of such mixtures.

For example, with the aid of the relevant amine adducts, phase mediatingeffects can be achieved, for example, in incompatible polyol mixtures,polyol-isocyanate mixtures or polyol-blowing agent mixtures (used, forexample, in manufacturing polyurethane).

In the following, the invention will be explained further based onexamples.

In substances that lack molecular uniformity, the indicated molecularweights represent averages. When titratable end groups are present, suchas acid, hydroxy or amino groups, the molecular weights are determinedby end-group determination by ascertaining the acid number, OH number orthe amine number. In the case of compounds to which an end groupdetermination is not applicable, the molecular weight is determined bylight scattering.

Unless performed differently, statements in parts refer to parts byweight and statements in percentages, to percentages by weight.

PREPARATION PROCEDURES

a) General Instructions for Producing Polyester Components fromLactones:

In a four-necked flask with agitator, thermometer, reflux cooler andnitrogen inlet tube, substances R1a) to T1c) are placed and heated to100° C. with agitation under N2 gas. Then the catalyst is added andheating under N2 gas is continued to T1. Agitation is continued at thistemperature until the FK>99% is achieved.

b) General Instructions for Producing Polyester Components fromHydroxycarboxylic Acids:

In a four-necked flask equipped with agitator, thermometer, refluxcooler and nitrogen inlet tube, substances R1a) to R1c) are placed andheated to 100° C. with agitation under N2 gas.

At 100° C. the catalyst is added and a distillation trap is attached.

Heating is continued, and the water released is removed by thedistillation trap.

The reaction temperature is adapted to the water released and goes toT1.

When no further water is released, the reaction is complete.

c) General Instructions for Producing Polyester Components from Diolsand Dicarboxylic Acids:

In a four-necked flask equipped with agitator, thermometer, refluxcooler, distillation trap and nitrogen inlet tube, substances R1a) toR1c) are weighed in together with the catalyst and heated under N2 gas.The water of reaction produced is collected via the distillation trap.

The reaction temperature is adapted to the water released and goes toT1. When no further water is released, the reaction is complete.

d) General Instructions for Producing Intermediates:

Reaction of Polyesters with Amines with Splitting Off of Water:

In a four-necked flask equipped with agitator, thermometer, refluxcooler, distillation trap and nitrogen inlet tube, substances R2a) andR2b) are placed and heated under N2 gas. The water of reaction producedis collected via the distillation trap. The reaction temperature isadapted to the water released and goes to T1. When no further water isreleased, the reaction is complete.

e) General Instructions for Producing Intermediates:

Reaction of Polyesters with Amines with Splitting Off of Water:

In a four-necked flask equipped with agitator, thermometer, refluxcooler and nitrogen inlet tube, reaction component R2a) is placed andheated under N2 gas to reaction temperature T1. Reaction component R2b)is added during the preset time X1. The consecutive reaction period is 1h at T1.

f) General Production Instructions According to Reaction Variant i):

In a four-necked flask equipped with agitator, thermometer, refluxcooler and nitrogen inlet tube, reaction component R3a) is placed andheated under N2 gas to T2. The consecutive reaction period is over timeX2 at T2.

Then reaction component 3b) is added. Agitation is performed for time X1at T1. Then reaction component 3c) is added and heating is performedunder N2 gas to T2. The consecutive reaction period is over period X2 atT2. In the case of a further reaction with a raw material 3d), this isadded 1 h after 3c) and the consecutive reaction period is addedappropriately.

g) General Production Instructions According to Reaction Variant i) withIntermediate Product:

In a four-necked flask equipped with agitator, thermometer, refluxcooler and nitrogen inlet tube, reaction component 3a) is placed andheated to 100° C. with agitation under N2 gas.

Then reaction component 3b) is added at 100° C., then heating to T1 andagitation for time X1 is performed.

h) General Production Instructions According to Reaction Variant ii):

In a four-necked flask equipped with agitator, thermometer, refluxcooler and nitrogen inlet tube, reaction component 3a) is placed andheated to T1. Component 3b) is added in X1. After addition, 0.5 h ofconsecutive reaction takes place at T1. Then reaction component 3c) isadded, and heating is performed under N2 gas to T2. This is followed bya consecutive reaction time X2 at T2.

i) General Production Instructions According to Reaction Variant (ii)with Intermediate Product:

In a four-necked flask equipped with agitator, thermometer, refluxcooler and nitrogen inlet tube, reaction component 3a) is placed andheated to T1. Component 3b) is added in time period X1. Then heating toT2 is performed under N2 gas. The consecutive reaction time at T2 isthen X2.

j) General Production Instructions According to Reaction Variant iii):

In a four-necked flask equipped with agitator, thermometer, refluxcooler and nitrogen inlet tube, reaction component 3a) is placed andheated to T1 under N2 gas. Then reaction components 3b) and 3c) areadded separately each in X1. Then heating to T2 is performed and themixture is heated at T2 for the time period X2.

k) General Production Instructions According to Reaction Variant iv):

In a four-necked flask equipped with agitator, thermometer, refluxcooler and nitrogen inlet tube, reaction components 3a) and b) areplaced and heated to T1 under N2 gas.

Component 3c) is added in X1. Then 0.5 h of consecutive reaction takesplace at T1. Then reaction component 3d) is added and heating under N2gas is continued further to T2. Then consecutive reaction X2 isperformed at T2 under N2 gas.

Preparation of a Comparison Example EX1 not According to the Invention:

In a four-necked flask equipped with an agitator, thermometer, refluxcooler and inlet tube, 4.4 parts of hydroxyethylacrylate with 66.00parts caprolactone and 28.3 parts valerolactone with 0.01% monobutyltinoxide and 0.1% hydroquinone are heated under an air atmosphere andagitation to 120° C. to obtain a polyester with Mn 2100. After 12 h at120° C., cooling to 65° C. is performed. Then 6.91 partspolyethyleneimine, MW 2000, are added. The reactants are then agitatedfor 2 h at 65° C.

Preparation of a Comparison Example EX2 not According to the Invention,Comparable to E14, but without Component C:

In a four-necked flask equipped with an agitator, thermometer, refluxcooler and inlet tube, 94.3 parts of polyester B10 are placed, heated to100° C., and 5.7 parts of a polyethyleneimine with MW 2000 are added.Then heating is performed to 140° C. and agitation continued for 2 h atthis temperature.

Table of polyester components Bsp HV R 1a) % R1a) R 1b) % R1b) R 1c) %R1c) Kat % T1 MG B1 a) LS 20.05 CAPA 79.80 ZB 0.15 190.00 1000 B2 a) HSS22.40 CAPA 77.50 ZB 0.10 190.00 1500 B3 a) LS 14.90 CAPA 85.00 ZB 0.10190.00 1300 B4 a) RFS 19.90 CAPA 79.80 ZB 0.30 190.00 1500 B5 a) RFS15.40 CAPA 84.30 ZB 0.30 190.00 2000 B6 a) LS 11.30 CAPA 77.30 VAL 11.30IPT 0.50 190.00 1770 B7 a) LS 14.00 CAPA 71.70 VAL 14.00 IPT 0.30 190.001400 B8 a) LS 19.90 CAPA 59.80 VAL 19.90 IPT 0.40 190.00 1000 B9 a) HSS32.40 CAPA 67.30 ZB 0.30 190.00 1000 B10 a) LS 9.88 CAPA 90.10 ZB 0.02190.00 2000 B11 a) LS 13.70 CAPA 85.80 IPT 0.50 190.00 1500 B12 b) RFS99.00 PTS 1.00 170.00 1500 B13 b) HSS 99.00 PTS 1.00 170.00 1200 B14 b)RFS 49.50 HSS 49.50 PTS 1.00 170.00 3000 B15 c) LS 22.00 BDO 29.50 ADS48.20 DBS 0.30 160.00 900 B16 c) ADS 62.80 BDO 36.20 PTS 1.00 160.003500 B17 c) PSA 66.40 BDO 33.40 DBS 0.20 160.00 1300 B18 a) LS 8.7 Capa73.8 VAL 17.3 IPT 0.2 160.0 2100 B19 a) LS 11.3 CAPA 88.7 IPT 0.5 1901770 B20 a) LS 14 CAPA 85.7 IPT 0.3 190 1400 B21 a) LS 19.9 CAPA 79.7IPT 0.4 190 1000 B22 a) LS 8.7 CAPA 91.1 IPT 0.2 190 2100 Bsp = example;HV = production instructions; KAT = catalyst; T(number) temperature asdescribed in the HV; LS = lauric acid; HSS = hydroxystearic acid, RFS =castor oil fatty acid; CAPA = epsilon-caprolactone; VAL =delta-valerolactone; BDO = butanediol; ADS = adipic acid; ZB = zirconiumbutylate; PT = isopropyl titanate; PTS = p-toluenesulfonic acid

Table of intermediate products Bsp HV R 2a) % R2a R 2b % R2b T1 X1 Z1 d)BT2 94.00 TEPA 6.00 160° C. 180 Z2 d) BT2 93.50 DETA 6.50 160° C. 150 Z3d) BT2 93.90 PEI 300 6.10 160° C. 150 Z4 d) BT3 94.70 TETA 5.30 160° C.180 Z5 e) PEI 62.30 PGE 37.70 100 150 1200 Z6 e) DETA 28.60 EPN 71.40100 120 Z7 e) TETA 44.20 EPN 55.80 100 120 Z8 e) PEI 300 61.70 PGE 38.30100 150 Z9 e) TEPA 60.00 EPN 40.00 100 150 X (number) = reaction timedescribed in the HV; TETA = triethylenetetramine; TEPA =tetraethylenepentamine; DETA = diethylenetetramine; PEI (number) =polyethyleneimine (MW); IPA = n-3-aminopropylimidiazole; EPN =epoxypropylneodecanoate; PGE = phenylglycidyl ether; BA = butylacrylate.

Table of end products Ti X1 T2 X2 Bsp HV R 3a) % 3a) R 3b) % 3b) Rc) %R3c) Rd) % R3d) [° C.] [min] [° C.] [min] E1 i) B1 81.70 Z6 18.30 100 20140 120 E2 i) B2 90.60 Z8 9.40 100 20 140 120 E3 i) B2 94.80 Z7 5.20 10020 140 120 E4 f) B2 84.50 PEI 1200 7.70 EPN 7.80 100 30 140 180 E5 h)PEI 8.70 EPN 8.90 B3 82.40 100 120 140 180 2000 E6 h) PEI 7.70 EHA 7.80B4 84.50 100 120 140 120 1200 E7 i) B4 87.00 Z9 13.00 100 20 130 180 E8i) B5 91.70 Z5 8.30 100 20 130 180 E9 i) B6 88.80 Z9 11.20 100 20 140120 E10 i) B7 84.60 Z9 15.40 100 20 140 120 E11 h) PEI 8.70 EPN 8.80 B782.50 100 120 120 180 1200 E12 h) PEI 6.80 PC 3.4 B8 86.40 CGE 3.4 100120 140 180 800 E13 i) B9 81.70 Z9 18.30 100 20 140 120 E14 k) B10 60.00PEI 2000 9.80 PGE 11.60 B10 18.60 100 60 120 180 E15 i) B11 87.00 Z913.00 100 20 140 180 E16 h) PEI 5.70 PGE 3.00 B11 91.30 100 120 140 1802000 E17 i) Z1 92.40 EHA 7.60 80 60 E18 i) Z2 86.00 LA 14.00 80 60 E19i) Z3 93.30 EPN 6.70 80 60 E20 i) Z4 95.80 MSA 4.20 80 60 E21 j) B1085.00 DMDPTA 8.10 PGE 6.90 60 60 120 240 E22 f) B14 93.60 PEI 300 3.2 PC2.0 CGE 1.2 100 30 140 180 E23 f) B16 95.60 DETA 1.7 EHA 2.70 100 30 120240 E24 f) B17 88.50 DETA 3.9 LA 7.60 100 30 120 240 E25 j) B1 65.80TETA 9.70 EHA 25.50 100 60 120 240 E26 k) B15 90.30 PEI 300 6.5 EHA 2.30MSA 1.20 100 30 120 120 E27 f) B18 78.6 PEI 2000 9.7 EHA 11.7 100 30 140120 i) B19 88.8 Z9 11.2 100 20 140 120 E29 i) B20 84.6 Z9 15.4 100 20140 120 E30 h) PEI1200 8.7 EPN 8.8 B20 82.5 100 120 120 180 E31 h)PEI800 6.8 PC 3.4 B21 86.4 CGE 3.4 100 120 140 180 E32 f) B22 78.6PEI2000 9.7 EHA 11.7 100 30 140 120 E33 h) PEI1200 7.70 CGE 7.8 B4 84.50100 120 140 120 MSA = maleic anhydride; EHA = ethylhexyl acrylate; LA =lauryl acrylate; PC = propylene carbonate, DMDPTA =dirnethyldipropylenetriamine, CGE = o-cresylglycidyl ether All endproducts listed in the table are solvent-free and solid at 30° C.

Applications Technology Testing

The relevant amine adducts (polymers) are used, among other things, aswetting and dispersing agents for producing pigment concentrates, paintsystems and ink jet systems.

Applications Technology Testing in Ink Jet Systems:

Operating Equipment:

Shaker: LAU Paint Shaker DAS H [/A]200-K

Luster/haze measurement:

-   -   Trigloss, (Byk Gardner)    -   Measurement angle 20°

Substances for applications technology testing:

-   Vinnol solution: 75% butylglycol acetate+2-% cyclohexanone+5% Vinnol    15/45;-   Vinnol 15/45: Copolymer of approx. 85% by weight vinyl chloride and    approx. 15% by weight vinyl acetate; manufacturer: Wacker-   Novoperm P-M3R: P.Y. 139-   InkJet Magenta E02: P.R. 122 Type A-   Irgalite Blue P.B. 15:4, Type B-   NiPex 90 p.Bk-7, pH=9.0

Method of Operation:

-   -   For producing the pigment concentrates: weigh items 1-4 into a        100 ml glass flask and mix. Then add 100 g zirconium beads        (0.4-0.5 mm).    -   Disperse premixed pigment concentrates for 960 minutes in a        vibrating shaker at cooling level 3    -   Screen pigment concentrate into 50 ml glass bottles.

After storage overnight and after storage for one week at 40° C.,determine the viscosities using the Stress Tech instrument.

The concentrates are applied to PU film with 25 μm wet film layerthickness.

The color intensity and transparency are evaluated visually on the film;for the luster and haze measurement, the films are placed on blackcardboard and measured.

Formulation 1—Pigment concentrate based on Novoperm Yellow P-M3R

Item No. Raw material [g] 1 VINNOL solution 15.0 2 Butylglycol acetate25.9 3 Additive 2.1 4 Novoperm Yellow P-M3R 7.0 50.0 Additive additionrate [% s.o.p.] 30.0

Formulation 2—Pigment concentrate based on Ink Jet Magenta E 02

Item No. Raw material [g] 1 VINNOL Solution 15.0 2 Butylglycol acetate25.9 3 Additive 2.1 4 Ink Jet Magenta P-M3R 7.0 50.0 Additive additionrate [% s.o.p.] 30.0

Formulation 3—Pigment concentrate based on Irgalite Blue GLVO

Item No. Raw material [g] 1 VINNOL solution 15.0 2 Butylglycol acetate27.2 3 Additive 1.8 4 Irgalite Blue GLVO 6.0 50.0 Additive addition rate[% s.o.p.] 30.0

Formulation 4—Pigment concentrate based on NiPex 90

Item No. Raw material [g] 1 VINNOL solution 15.0 2 Butylglycol acetate26.0 3 Additive 3.0 4 NiPex 90 6.0 50.0 Additive addition rate [%s.o.p.] 50.0

Results:

Color intensity+transparency: 1-5 (1=good, 5=poor)

Novoperm P-M3R Ink Jet Magenta E02 Visco 1 Visco 1 W W Addi- Visco 40°C. Color = Trans = Visco 40° C. Color = Trans = tive (mPas) (mPas)Luster Haze intensity parency (mPas) (mPas Luster Haze intensity parencyEX1* 19 29 89 — 5 4 418 489 91 — 4 4 E4 11 14 95 — 1 1 309 386 97 — 2 2E7 16 18 92 — 2 1 323 396 92 — 2 2 E19 13 15 95 — 1 2 311 401 93 — 2 2Addi- Visco Visco 1 Color Trans = Visco Visco 1 Color Trans = tive(mPas) W Luster Haze intensity parenz (mPas) W Luster Haze intensityparency EX1* 164 167 92 — 3 3 525 885 93 31 3 E4 103 135 98 — 1 1 31 9499 9 1 E7 142 148 97 — 1 2 174 324 96 21 2 E19 136 153 98 — 2 2 145 21499 99 1 *Not according to invention Visco = viscosity

Conclusion of Tests in Ink-Let Systems:

The particularly good quality of the polymers according to the inventionis demonstrated by their low viscosity, color intensity, transparencyand good luster.

An additional particular advantage of the polymers consists of theparticularly good incorporation in the binder solution.

Applications Technology Testing in Pigment Concentrates:

Working Equipment:

Dispermat CV

Trigloss, (Byk Gardner)

Scandex Vibrating Shaker

Substances for Applications Technology Testing:

Lamp black FW 200 → PB 7 Laropoal A81 → Aldehyde resin, manufacturerBASF Paraloid DM 66 → Thermoplastic acrylate resin TPA): manufacturerDOW Macrynal SM 510 → Acrylate resin 70% in; manufacturer Cytec DesmodurN75 → Aliphatic isocyanate, 75% in methoxypropyl acetate; manufacturerBayer Setalux 1756 V V65 → Acrylate resin 65%% in solvent naphtha;manufacturer Nuplex Setamine US 138 0 → Melamine resin 70% in n-butanol,manufacturer Nuplex Epikote 1001 → Epoxy resin 75% in xylene,manufacturer Brenntag Aradur 115 → Polyamidoamine; manufacturer HuntsmanDowanol PMA → Methoxypropyl acetate, manufacturer DOW Dowanol PM →Methoxypropanol, manufacturer DOW Solvesso 100 → Aromatic solvent fromExxon BYK 306/310/325 → Leveler additive, manufacturer BYK

Method of Operation:

Preparation of the Pigment Concentrates:

-   -   Weigh in the lacquer constituents in the indicated order (stir        briefly manually after each addition)    -   Dispermat CV/60 minutes/10,000 rpm (23 m/s) at 40° C. material        to be ground/glass beads (0.8-1.2 mm) 1:1 ratio (by weight)    -   Screen out the glass beads after dispersing    -   Visually evaluate the viscosity (after preparation, after 1 day)

Preparation of the Lacquer:

Incorporate the pigment concentrates into the different lacquer systemswith a Scandex vibrating shaker for 5 min

-   -   Pour the diluted lacquer onto PE film    -   Make an overall visual evaluation of transparency and optical        properties-1-5; (1=good, 5=poor)    -   Measure luster with Trigloss

Formulation of Pigment Concentrate

12.5% carbon black with 80% additive solid on pigment

Raw material [g] Laropal A81 60% in methoxypropyl acetate 54.1 DowanolPMA 23.4 Additive 100% 10.0 Lamp black FW 200 12.5 (pigment/binder ratio1/3.5) 100.0

Formulation of Pigment Concentrate

15% carbon black with 60% additive solid on pigment

Raw material [g] Laropal A81 60% in methoxypropyl acetate 53.1 DowanolPMA 22.9 Additive 100% 9.0 Lamp black FW 200 15.0 (pigment/binder ratio1/3.5) 100.0

Formulations of clear lacquer with finalization of the pigmentconcentrate in clear lacquer

TPA

Paraloid B66 Paraloid B66 (50% in xylene) 70.0 Diisodecyl phthalate 2.0Xylene 21.8 Dowanol PMA 6.0 BYK-306 0.2 100.0 Clear lacquer (ParaloidB66) 27.5 Pigment concentrate 2.5 30.0 Incorporation of pigmentconcentrate on vibrating shaker Xylene 30.0

2K-PUR

Macrynal SM 510/Desmodur N Macrynal SM 510 (70% in butyl acetate) 75.0Dowanol PMA 5.0 Solvesso 100 5.0 Xylene 6.9 Butyl acetate 8.0 BYK-3060.1 100.0 Hardener solution 2:1 (weight) Desmodur N75 50.0 Butyl acetate17.5 Solvesso 100 17.5 Dowanol PMA 5.0 Xylene 10.0 BYK-306 0.1 100.0Clear lacquer (Macrynal SM 510/Desmodur N 20.0 Pigment concentrate 2.022.0 Incorporation of pigment concentrate on vibrating shaker Hardenersolution 10.0

Acrylate/Melamine System

Setalux 1756/Setamine US 138 Setalux 1756 VV 65 60.0 Setamine US 13824.0 Solvesso 100 8.0 Xylene 7.8 BYK-310 0.2 100.0 Clear lacquer(Setalux 1756/Setamine US 138) 25.0 Pigment concentrate 2.0 27.0Incorporation of pigment concentrate on vibrating shaker Solvesso 1003.0

After 15 [min] flash-off time, the applied lacquer is baked on for 20min at 130° C.

2K Epoxide

Epikote 1001/Aradur 115 x 70 Epikote 1001 (75% in xylene) 60.0 Xylene17.0 Dowanol PM 12.8 n-Butanol 10.0 BYK-325 0.2 100.0 Hardener solution2:1 (weight) Aradur 115 x 70 35.5 Xylene 6.0 Dowanol PM 4.0 n-Butanol4.5 50.0 Clear lacquer (Epikote 1001/Aradur 115 x 70) 20.0 Pigmentconcentrate 2.0 22.0 Incorporation of pigment concentrate on vibratingshaker Hardener solution 10.0

Results:

Appearance in lacquer system: 1-5 (1=good, 5-poor)

Viscosity: hv=high-viscosity; mv=medium-viscosity; lv=low viscosityAppear.=appearance

Pigment pastes with 12.5% carbon black and 80% additive solid on pigment

Visco. Visco. . of of paste on paste disper- after 1 Baking lacquer/Baking lacquer/ 2K-PUR. SM 2K-PUR/Set. Addi- sion, day, acrylate alkyd510 1573 2K-epoxy tive visual visual Appear. Luster Appear. LusterAppear. Luster Appear. Luster Appear. Luster EX1* hv very hv 4 78 3 85 579 4 84 5 85 floccu- lated EX2* hv hv 4 81 4 83 4 85 3 85 4 82 E2 mv mv2 89 2 94 1 90 2 91 2 88 E4 mv lv 1 86 1 94 1 89 1 92 2 94 E5 mv mv 1 962 89 1 91 2 92 2 98 E8 lv lv 1 92 2 91 1 94 1 89 1 92 E14 very lv lv 194 1 95 1 92 1 93 2 89 E27 very lv very lv 1 98 1 96 1 95 1 98 1 95

Pigment pastes with 15% carbon black and 60% additive solid on pigment

Visco. Visco. of of paste on paste disper- after 1 Baking lacquer/Baking lacquer/ 2K-PUR. SM 2K-PUR/Set. Addi- sion, day, acrylate alkyd510 1573 2K-epoxy tive visual visual Appear. Luster Appear. LusterAppear. Luster Appear. Luster Appear. Luster EX1* cannot be cannot be —— — — — — — — — — made made EX2* cannot be cannot be — — — — — — — — — —made made E2 mv hv 2 87 3 89 3 84 2 90 3 88 E4 lv mv 3 82 2 93 2 87 1 872 90 E5 mv mv 2 89 2 91 3 89 2 86 3 86 E8 mv mv 2 86 3 89 2 91 2 89 2 89E14 lv lv 1 94 2 87 1 92 2 91 3 85 E27 very lv lv 1 96 1 95 1 94 1 94 191 *Not according to invention

Conclusions from Tests on Pigment Concentrates for Different LacquerSystems:

The relevant amine adducts are characterized by particularly goodcompatibility in the various lacquer systems. Corresponding pigmentpastes have low viscosities and can be incorporated excellently. It ispossible without further effort to produce pigment pastes with higherpigment contents. The outstandingly good luster and the excellent shelflife of the pigment concentrates are particularly noteworthy.

1. A process for preparing an amine adduct, in which a polyamine component (A), a polyester component (B) and a hydrocarbon component (C) are reacted in weight ratios of (A):(B)=1:1000 to 1:1 (A):(C)=1:100 to 100:1 and (B):(C)-2:1 to 50:1 in that according to reaction variant i) first a reaction intermediate (A-B) is produced from the polyamine component (A) and the polyester component (B), which is subsequently reacted with the hydrocarbon component (C) or according to reaction variant ii) first a reaction intermediate (A-C) is formed from the polyamine component (A) and the hydrocarbon component (C) and this is subsequently reacted with the polyester component (B) or according to reaction variant iii) first the polyamine component (A) is reacted simultaneously with the polyester component (B) and the hydrocarbon component (C) wherein the polyamine component (A) is present in the form of organic polyamine compounds (A′), which in each case have at least three amino groups (A′+) selected from primary and secondary amino groups, in each case reactive with both the polyester component (B) and the hydrocarbon component (C), the polyester component (B) is present in the form of polyester compounds (B′), which in each case contain no primary amino groups and no secondary amino groups, in each case have at least three ester groups, and in each case contain a coupling group (B′+) present as a carboxyl group or carboxylic acid anhydride group, reactive with primary and/or secondary amino groups, and the hydrocarbon component (C) is present in the form of branched or unbranched, saturated or unsaturated hydrocarbon compounds (C′) each having a linking group (C′+), in each case having no primary amino groups, in each case having no secondary amino groups, in each case having no carboxyl groups and in each case having no carboxylic acid anhydride groups, and in each case having an overall ratio of carbon atoms to hetero atoms selected from the group of elements O, N, P, S, and Si of at least 2:1, wherein the linking groups (C′+) in each case have the characteristic of reacting with primary amino groups with formation of secondary amino groups and/or with secondary amino groups with formation of tertiary amino groups, and also in each case are present in the form of an epoxy function of general formula (I)

with R¹, R², and R³ in each case the same or different and each independently of one another is represented by H and/or by a saturated, branched or unbranched C₁-C₁₂ hydrocarbon moiety, wherein the amine adduct is obtained in solid form at room temperature in each case and has a melting range of 30 to 200° C. and the reaction of the polyamine component (A), the polyester component (B) and the hydrocarbon component (C) takes place in that for each weight unit of polyester component (B), a maximum of 0.8 weight units of other components that do not belong to any of the components (A), (B) or (C) are present.
 2. (canceled)
 3. The process according to claim 1, wherein the reaction of (A), (B) and (C) is performed in weight ratios of (A):(B)=1:100 to 1:4 and (A):(C)-1:10 to 10:1.
 4. The process according to claim 1, wherein the reaction of the polyamine component (A), the polyester component (B) and the hydrocarbon component (C) takes place in such a manner that for each weight unit of polyester component (B), a maximum of 0.2 units by weight of other components are present, which do not belong to any of the components (A), (B) or (C).
 5. The process according to claim 1, wherein the reaction of the polyamine component (A), the polyester component (B) and the hydrocarbon component (C) takes place in the absence of organic solvents.
 6. The process according to claim 1, wherein at least 50% by weight of the polyester compounds (B′) used is present in the form of linear, monocarboxy-functional caprolactone polyesters, which optionally in each case have a weight-average molecular weight of 500 to 10,000.
 7. The process according to claim 1, wherein the hydrocarbon component (C) contains at least 30% by weight, of unsaturated C₆-C₅₀ hydrocarbon compounds (C′), which in each case contain at least one aryl and/or one alkylaryl group.
 8. The process according to claim 1, wherein the hydrocarbon component (C) contains at least 30% by weight, of C₁₀-C₇₀ hydrocarbon compounds (C′), which in each case contain at least one branched alkyl and/or one branched alkenyl moiety.
 9. The process according to claim 1, wherein components (A), (B) and (C) are used respectively in stoichiometric ratios such that altogether at least 50 mol %, of the totality of the reactive amino groups (A′+) of the polyamine compounds (A′) used are reacted with the polyester compounds (B′) and/or with the hydrocarbon compounds (C′).
 10. The process according to claim 1, wherein the polyester component (B) and the hydrocarbon component (C) do not react with one another under the reaction conditions of the reaction.
 11. An amine adduct prepared according to the method of claim
 1. 12. The amine adduct according to claim 11, which is suitable as a wetting and dispersing agent, optionally for lacquer and plastics applications.
 13. A process for utilizing the amine adduct produced according to the method of claim 1, as an additive, which is optionally used as a wetting and dispersing agent, in coatings, in lacquers, in plastics, in pigment pastes, in sealants, in cosmetics, in ceramics, in adhesives, in potting compounds, in pigment-containing compounds for flat screen technology, in filling compounds, in printing inks and/or in inks.
 14. Mixture of solids containing particles and/or fibers treated with the amine adduct according to claim
 1. 15. Lacquer and/or plastic containing the amine adduct according to claim
 1. 16. The process according to claim 1, wherein the reaction of (A), (B) and (C) is performed in weight ratios of (A):(B)=1:25 to 1:7 and (A):(C)=1:2 to 2:1.
 17. The process according to claim 1, wherein 70 to 100% by weight of the polyester compounds (B′) used is present in the form of linear, monocarboxy-functional caprolactone polyesters, which optionally in each case have a weight-average molecular weight of 500 to 10,000.
 18. The process according to claim 1, wherein the hydrocarbon component (C) contains 50 to 100% by weight of unsaturated C₆-C₅₀ hydrocarbon compounds (C′), which in each case contain at least one aryl and/or one alkylaryl group.
 19. The process according to claim 1, wherein the hydrocarbon component (C) contains 50 to 100% by weight of C₁₀-C₇₀ hydrocarbon compounds (C′), which in each case contain at least one branched alkyl and/or one branched alkenyl moiety.
 20. The process according to claim 1, wherein components (A), (B) and (C) are used respectively in stoichiometric ratios such that altogether 70 to 100 mol % of the totality of the reactive amino groups (A′+) of the polyamine compounds (A′) used are reacted with the polyester compounds (B′) and/or with the hydrocarbon compounds (C′).
 21. A process for utilizing the solid amine adduct produced using the method according to claim 1, for applications for which exclusively solid additives can be used, wherein these applications exist in the form of uses for thermoplastic processing, powder lacquer applications, duroplast applications, toner applications or uses for solid pigment preparations. 